TWI612029B - 金屬化配位體,觸媒組成物,及其在乙烯之低聚合作用中之用途 - Google Patents
金屬化配位體,觸媒組成物,及其在乙烯之低聚合作用中之用途 Download PDFInfo
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- TWI612029B TWI612029B TW103104268A TW103104268A TWI612029B TW I612029 B TWI612029 B TW I612029B TW 103104268 A TW103104268 A TW 103104268A TW 103104268 A TW103104268 A TW 103104268A TW I612029 B TWI612029 B TW I612029B
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- Prior art keywords
- compound
- group
- pnpnh
- ethylene
- catalyst composition
- Prior art date
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000005977 Ethylene Substances 0.000 title claims abstract description 32
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 17
- 239000012190 activator Substances 0.000 claims abstract description 13
- 239000003426 co-catalyst Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 66
- 125000004122 cyclic group Chemical group 0.000 claims description 44
- 239000011651 chromium Substances 0.000 claims description 41
- 239000000470 constituent Substances 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- -1 Methyl fluorenyl Chemical group 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004437 phosphorous atom Chemical group 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 5
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- GPEHQHXBPDGGDP-UHFFFAOYSA-N acetonitrile;propan-2-one Chemical compound CC#N.CC(C)=O GPEHQHXBPDGGDP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 claims description 2
- TZJOIDXKFOTKCW-UHFFFAOYSA-N n-cyclohexylcyclohexanamine;5-[(2-methylpropan-2-yl)oxy]-5-oxo-2-(phenylmethoxycarbonylamino)pentanoic acid Chemical compound C1CCCCC1NC1CCCCC1.CC(C)(C)OC(=O)CCC(C(O)=O)NC(=O)OCC1=CC=CC=C1 TZJOIDXKFOTKCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical group [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims description 2
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical group [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims 1
- 238000001465 metallisation Methods 0.000 abstract description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 30
- 101150065749 Churc1 gene Proteins 0.000 description 30
- 102100038239 Protein Churchill Human genes 0.000 description 30
- 239000002904 solvent Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 125000005023 xylyl group Chemical group 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- MJXUFBUYCLOLBZ-UHFFFAOYSA-N C(C)(=N)N.CC(=O)C Chemical compound C(C)(=N)N.CC(=O)C MJXUFBUYCLOLBZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GYVCVTQHUUFHPO-UHFFFAOYSA-N [Cr]C1=CC=CC=C1 Chemical compound [Cr]C1=CC=CC=C1 GYVCVTQHUUFHPO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- PFTYFFFXKWUHOP-UHFFFAOYSA-N diethyl(2,2,2-trichloroethyl)alumane Chemical compound ClC(C[Al](CC)CC)(Cl)Cl PFTYFFFXKWUHOP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- JQUZTGJSSQCTPV-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C1C=CC=[C-]1 JQUZTGJSSQCTPV-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004792 aryl magnesium halides Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910001320 chromium hydride Inorganic materials 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WLTSEWGSVKQUDL-UHFFFAOYSA-N n-[phenyl-(propan-2-ylamino)phosphanyl]propan-2-amine Chemical compound CC(C)NP(NC(C)C)C1=CC=CC=C1 WLTSEWGSVKQUDL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- LOFJKBAHPJENQS-UHFFFAOYSA-N tris(oxomethylidene)chromium Chemical compound O=C=[Cr](=C=O)=C=O LOFJKBAHPJENQS-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract
本發明關於乙烯之低聚合作用之方法,其包含將觸媒組成物施加至乙烯之氣相中及進行低聚合作用,其中該觸媒組成物包含(a)鉻化合物、(b)金屬化配位體、及(c)活化劑或共觸媒;且關於觸媒組成物以及金屬化配位體。
Description
本發明關於一種乙烯之低聚合作用之方法,在低聚合作用中所使用之觸媒組成物,以及在該觸媒組成物中所使用之金屬化配位體。
具有通用結構PNPNH之化合物為熟知的配位體系統,其可成功地用在乙烯之低聚合作用的觸媒中。該等化合物在此係作為欲與(較佳為)鉻觸媒反應之配位體。與適合的共觸媒(cocatalyst)一起,此系統有效於乙烯之二-、三-及/或四聚合作用。
例如,EP 2 239 056 B1說明一種觸媒組成物及一種乙烯之二-、三-及/或四聚合作用之方法。觸媒組成物包含鉻化合物、通用結構R1R2P-N(R3)-P(R4)-N(R5)-H之配位體及充當活化劑之共觸媒。配位體的取代基R1、R2、R3、R4和R5係獨立選自一些官能基,其包含(尤其為)C1-C10-烷基、芳基和經取代之芳基。鉻來源係選自CrCl3(THF)3、
乙醯丙酮Cr(III)、辛酸Cr(III)、Cr-六羰基、2-乙基己酸Cr(III)和(苯)三羰基鉻,其中THF為四氫呋喃。共觸媒或活化劑係選自三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、三氯三乙基化二鋁(ethylaluminum sesquichloride)、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷(〝MAO〞),或包含前述中之至少一者的組合,較佳甲苯。
觸媒組分的較佳選擇包含CrCl3(THF)3作為鉻來源、三乙基鋁作為活化劑及(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H作為催化活性錯合物之配位體,如下文所示,其中Ph為苯基及i-Pr為異丙基。此配位體係以典型的PNPN-H-主鏈為特徵,這就是為什麼此類別的化合物常被稱〝PNPNH-配位體〞,而不論其取代基的確切性質。
WO 2009/006979 A2說明已在EP 2 239 056 B1中揭示之通用類型的實質上經改質之觸媒系統。該等經改質之系統係利用相同的PNPNH-類型配位體。然而,現將〝改質劑〞添加至系統中,該劑係選自(但不限於)類型[H4E]X、[H3ER]X、[H2ER2]X、[HER3]X或[ER4]X之銨或鏻鹽,其中E為N或P,X為Cl、Br或I,及R為烷基、環烷基、醯基、芳基、烯基、炔基及類似者。
在WO 2009/006979 A2中所揭示之較佳的具體實例包含例如改質劑,諸如氯化四苯基鏻(tetraphenylphosphonium chloride)、氯化四乙基銨單水合物(tetraethylammonium chloride monohydrate)、三乙胺鹽酸鹽(triethylamine hydrochloride)等等。亦可有利地使用
氯化十二烷基三甲基銨(dodecyltrimethylammonium chloride)作為〝類型[ER4]x〞改質劑,由於其低價位、貨源充足及在反應溶液中良好的溶解度。
事實上,PNPNH配位體的特定設計之配位行為主要為催化活性鉻錯合物之高選擇性的緣由。高產物選擇性對工業方法的經濟可行性顯然非常重要。
當然,高選擇性直接造成低聚合工業方法中最少的非所欲副產物。因此顯然觸媒的〝關鍵成分〞必須以具有最高可能品質的工業規模製造。
再者,用於觸媒組成物之配位體的製備方法尤其應具有成本效益、容易且快速,且應得到高純度。
用於製備PNPNH配位體之實驗室程序得到良好品質的材料。
在乙烯三聚合成1-己烯之標準化觸媒試驗中,使用來自實驗室小型規模合成的配位體有可能輕易獲得99.0-99.3%之1-己烯純度的91-93重量百分比之1-己烯總產率,幾乎沒有任何可檢測之蠟/聚合物形成。
然而,當轉移成工業規模時,此實驗室程序經常需要一些修改,以便符合由工業環境之邊界條件強加的要求。例如,為了避免在反應物料中的熱點,可能最好改變一些成分的給量順序及/或給量速度。此外,就工業規模,低至-40℃之反應溫度最有可能是不利的或甚至是行不通的。而且,可能必須使溶劑再循環,導致需要改變溶劑的性質或使用溶劑混合物。
即使針對工業規模最適化配位體製造方法之後,但是似乎不可能達到與使用實驗室程序所合成之產物相比的配位體品質,亦即純度。
在所有已知的工業規模之乙烯低聚合方法中最嚴重的問題之一為長鏈副產物的形成,諸如蠟和聚乙烯。此顯然導致頻繁的設備結垢,諸如反應器內表面、熱交換器等等。而且,蠟或聚合物形成可導致配管、閥、幫浦和其他設備堵塞,造成頻繁的工廠停機以洗淨/清潔及維護必要的設備。
必須將可量測之蠟/聚合物形成率考慮在商業的乙烯低聚合工廠之設計中。該等非所欲副產物之適當的最小化分量及處置程序是不可避免的,以容許商業上成功的工廠操作。
如上文已指出,應留意高選擇性直接造成此工業方法中最少的非所欲副產物,〝關鍵成分〞(亦即尤其為配位體)必須以具有最高可能品質的工業規模製造。
因此希望提供一種乙烯之低聚合作用之方法,其容許使用包含配位體之觸媒組成物,該配位體可以安全且容易的方式以高純度製得及導致該方法具有低的蠟/聚合物形成率。進一步的目的係提供各自的觸媒組成物,其可成功地利用在乙烯之低聚合作用中。
再者,可有利地提供可用於觸媒組成物中的金屬化配位體,以及其製備方法。
本文揭示一種乙烯之低聚合作用之方法,其包含將觸媒組成物與乙烯之氣相在有效使乙烯低聚合之條件下接觸,其中觸媒組成物包含(a)鉻化合物,(b)金屬化PNPNH化合物,其中PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從PNPNH-結構中之一或多種組成化合物形成,及(c)活化劑或共觸媒。
在另一具體實例中,用於乙烯之低聚合作用之觸媒組成物包含(a)鉻化合物,(b)金屬化PNPNH化合物,其中PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物其中
PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從PNPNH-結構中之一或多種組成化合物形成,及(c)活化劑或共觸媒。
在又另一具體實例中,一種使以下通式之化合物金屬化之方法,R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從PNPNH-結構中之一或多種組成化合物形成,該方法包含以下步驟:(i)將PNPNH化合物溶解在溶劑中,獲得溶液;(ii)使PNPNH化合物在溶液中金屬化,及(iii)使金屬化化合物沉澱、自溶劑分離且隨意地以溶劑清洗。
亦揭示以前述方法所獲得的金屬化化合物。
一種乙烯之低聚合作用之方法,其容許使用包含配位體之觸媒組成物,該配位體可以安全且容易的方式以高純度製得,及導致該方法具有低的蠟/聚合物形成
率,以乙烯之低聚合作用之方法達成,該方法包含將觸媒組成物施加至乙烯之氣相中及進行低聚合作用,其中觸媒組成物包含(a)鉻化合物、(b)如本文所述之金屬化配位體(化合物)、及(c)活化劑或共觸媒。
低聚合作用較佳地在1至200巴(bar)之壓力下進行,較佳為10至50巴。
低聚合作用較佳地在從10至200℃之溫度下進行,較佳為20至100℃。
該方法較佳地係連續或分批(batchwise)進行。
平均滯留時間較佳地從20分鐘至20小時,較佳為1至4小時。
一種用於乙烯之低聚合作用之觸媒組成物包含鉻化合物、如本文所述之金屬化配位體、及活化劑或共觸媒。
鉻化合物更佳地係選自有機或無機鹽、配位錯合物、及Cr(II)或Cr(III)之有機金屬錯合物。
甚至更佳的鉻化合物係選自CrCl3(THF)3、乙醯丙酮Cr(III)、辛酸Cr(III),六羰基鉻、2-乙基己酸Cr(III)和(苯)三羰基鉻。
亦較佳地,活化劑或共觸媒係選自三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、三氯三乙基化二鋁(ethyl aluminum sesquichloride)、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷(MAO),或包含前述中之至少一者的組合,較佳甲苯。
一種使以下通式之PNPNH化合物金屬化之方法R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,該環系統係藉由取代而從PNPNH-結構中之一或多種組成化合物形成,該方法包含以下步驟:(i)將PNPNH化合物溶解在溶劑中;(ii)將PNPNH化合物金屬化;及(iii)將金屬化化合物單離,例如藉由使步驟b)中所獲得的金屬化化合物沉澱、自溶劑分離且隨意地以溶劑清洗。
R1、R2、R3、R4和R5較佳地選自氯基(chloro)、胺基、三甲基矽基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基(benzyl)、甲苯基(tolyl)和二甲苯基(xylyl)。
PNPNH化合物更佳地選自(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(第三丁基)-H和(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H。
在步驟(ii)中的金屬化較佳地藉由將有機金屬
化合物、鹼、鈉金屬或鉀金屬以等於或超過PNPNH化合物之莫耳濃度的量添加至步驟(i)中所獲得的溶液中。
更佳的金屬化作用係藉由添加下列者而達成:正丁基鋰、第二丁基鋰、第三丁基鋰、環戊二烯化鈉(sodium cyclopentadienide)、氫化鈉、胺化鈉、鹵化烷基鎂或鹵化芳基鎂(格任亞(Grignard)試劑)、雙(三甲基矽基)胺化鈉、二烷基鎂、二芳基鎂、三烷基鋁、二烷基鋅、鈉金屬或鉀金屬,較佳為正丁基鋰。
最後,說明以上述方法可獲得的金屬化化合物。
應瞭解如文中所使用之術語PNPNH代表通用結構R1R2P-N(R3)-P(R4)-N(R5)-H。
在本文所揭示之金屬化配位體可係以〝PNPN-M〞縮寫,M為用於金屬化作用之金屬。熟諳此項技術者應瞭解此式包含任何化合物,諸如[PNPN-M]2、[PNPN]2M、PNPNMR或PNPNMRR,R為任何適合的烷基或芳基取代基,其顯然取決於所使用之金屬化試劑之化學要求。例如,使用鋰的金屬化作用能得到具有式[PNPNLi]2之金屬化配位體,或使用鉻能得到[PNPN]2Cr之化合物,或使用二烷基鋅能得到PNPNM烷基之結構。
如所瞭解的是可利用PNPNH化合物之任何環狀衍生物,其中PNPN-單元的P或N原子中之至少一者為環員,或其中PNPN-H結構的P或N原子中之至少一者為環系統的一員之任何環狀衍生物,環系統係藉由取代而
從PNPNH-結構中之一或多種組成化合物形成,亦即藉由每一組成化合物在形式上消除兩個完整的基團R1-R5(如上文所定義)或H、一個來自兩個基團R1-R5(如上文所定義)之各者或完整的R1-R5(如上文所定義)之原子或H、及來自另一基團R1-R5(如上文所定義)之原子,及每一組成化合物以一個共價鍵連接在形式上因此產生的價數不飽和位置,以提供與最初存在於給定位置上相同的價數。在具體實例中,環係藉由取代一個PNPNH分子的組成中之一或多者(較佳為二者)而形成。換言之,環狀衍生物可包括藉由從一個PNPNH分子移除基團R1-R5(如上文所定義)中之二者或H(形成代替基團的共價鍵)所形成之環系統。環狀衍生物可包括藉由從一個PNPNH分子移除基團R1-R5(如上文所定義)中之二者的原子或H(形成代替原子的共價鍵)所形成之環系統。另一選擇地,環狀衍生物可藉由從一個PNPNH分子移除基團R1-R5(如上文所定義)中之一者或H及從相同的PNPNH分子移除基團R1-R5(如上文所定義)中之一者的原子或H(形成代替移除之基團及原子的共價鍵)而形成。
通常較佳的是,溶劑為非極性溶劑,較佳地選自芳族及/或脂族溶劑,較佳為甲苯、正己烷、環己烷和1-己烯。
用於步驟i)中溶解PNPNH化合物的較佳溶劑可選自甲苯、正己烷、環己烷、1-己烯,或包含前述中之至少一者的組合,較佳為甲苯。
在步驟iii)中的分離較佳地可藉由過濾或離心而達成。隨意的清洗可以純溶劑進行。
驚訝地發現金屬化配位體本身可用於催化乙烯之低聚合作用的觸媒組成物中,亦即配位體沒必要再質子化(reprotonation)及進一步整理(work-up)。
如下文所示,使用金屬化配位體代替PNPNH配位體雖然可能造成整體催化活性稍微下降,但是C6-選擇性及1-己烯純度大致不受影響而維持在高水平。然而,使用金屬化配位體具有非常簡單的配位體純化程序之優點,因為配位體純化已發生在金屬化配位體材料的沉澱期間。使用金屬化配位體導致乙烯之低聚合作用中有利的低
蠟/聚合物形成率,且尤其可在每當最高的特定生產力之達成並非最重要時使用。
在乙烯之低聚合作用中利用根據本發明所獲得的金屬化配位體,提供大幅減少的副產物蠟及聚乙烯形成,延長低聚合設備的運轉時間(time on stream),減少為了洗淨、清潔和維護的停機次數,減緩設備結垢,減少由於設備堵塞造成的意外的操作狀況之機會,及總之大體上改善工廠的操作性。
更驚訝的事實是發現沒有其他可能的〝關鍵因素〞候選者(亦即影響蠟/聚乙烯形成的關鍵因素)對聚合物形成顯示出任何顯著或可辨識的影響。此等更多的關鍵因素可為例如與被認為是趨向較佳的寡聚物之高選擇性的緣由之金屬環機制(metallocycle mechanism)、隨著觸媒組份而以微量引入的金屬雜質Fe、Ni、Ti、Zr等等、在反應器內表面上經表面誘發之非均質反應、氫化鉻種類、基聚合反應(radical polymerisation)機制或不利的鉻氧化態連結的內在機制原因。
如上文已指出,驚訝地發現金屬化化合物可藉由PNPNH化合物之金屬化作用而輕易地與雜質分離,因為金屬化種類在PNPNH化合物之製造方法及/或低聚合反應中典型使用的溶劑中經常顯示出差的溶解度。較佳的金屬化種類PNPN-M為那些M=Li、Mg、Na、K、Cr、Al和Zn之種類。雖然在上文提出金屬化試劑之特定實例,但是PNPN-Cr化合物可較佳經由各自的Mg-化合物
使用CrCl2(THF)2之轉金屬化作用(transmetalation)(在釋出MgCl2及2THF下)而獲得。Mg-金屬化化合物依次可藉由將PNPNH配位體與任何金屬化鎂化合物(諸如Mg-烷基或鹵化烷基鎂(諸如丁基乙基鎂或氯化異丁基鎂))反應而獲得。
本發明額外的優點及特徵現由以下的實施例章節例證。
將二氯苯膦(9.63毫升,71毫莫耳,溶解在50毫升二乙醚中)在0℃下經30分鐘期間添加至二乙醚(250毫升)中的異丙胺(30毫升,352毫莫耳)之攪拌溶液中。在總共攪拌72小時之後,將溶液過濾。將殘餘物以二乙醚清洗且在真空中移除溶劑。將剩餘油在0.2托(Torr)/76-78℃下蒸餾,得到具有33%產率(5.3公克)之無色液體。31P{H}NMR:49.0ppm。
將四氫呋喃(10毫升)中的NPN-種類(NPN-species)(2.4公克,10.7毫莫耳)之溶液逐滴添加至-40℃下在四氫呋喃(40毫升)中的三乙胺(6毫升)及氯二苯膦(2.36公克,10.7毫莫耳)之攪拌溶液中。在室溫下再攪拌24小
時之後,濾出三乙銨鹽,且將殘餘物溶解在正己烷中,再過濾且將溶液保持在-30℃下結晶。產率52%(2.3公克,5.6毫莫耳)。31P{H}NMR:41.2,68.4(寬峰)。
將Ph2PN(i-Pr)P(Ph)N(i-Pr)-H(8.70公克,21.35毫莫耳)溶解在15毫升甲苯中。在冷卻至-78℃之後,將正丁基鋰(12.8毫升,在正庚烷中的2.5M n-BuLi,32.0毫莫耳)添加至溶液中,造成顏色立即改變成橘/黃色。將溶液在室溫下再攪拌2小時且沉澱出無色固體。將沉澱物過濾且以5毫升甲苯清洗3次。在真空中移除剩餘溶劑,得到無色粉末。產量:6.73公克(76%)。分子量:414.39公克/莫耳[C24H29LiN2P2]。元素分析:計算值:C 69.56%,H 7.05% & N 6.76%;實測值:C 69.25%,H 7.06%,N 6.87%。熔點:187-189℃。1H NMR(THF-d8)δ=7.50-7.57(m,6H,芳基-H),7.20-7.34(m,6H,芳基-H),7.02(m,2H,芳族),6.93(m,1H,芳基-H),3,70(m,1H,CHCH3),3.58(m,1H,CHCH3),1.39(d,J=6.47Hz,3H,CHCH3),1.25(d,J=6.23Hz,3H,CHCH3),1.22(d,J=6.24Hz,3H,CHCH3),1.04(d,J=6.55Hz,3H,CHCH3);13C-NMR(THF-d8):δ=143.4,142.0,134.9,133.4,132.5,131.5,129.4,128.6,128.0,127.9,127.1,125.2(芳族),54.6,54.0(CHCH3),31.0,26.7(CHCH3);
31P{H}NMR(THF-d8):δ=40.6(br),100.1pp,(d,2JP-P=24.6Hz)。
額外的金屬化配位體係藉由使用鋅、鎂、鉻和鋁金屬化劑而製得。
Ph2PN(i-Pr)P(Ph)N(i-Pr)ZnEt之製備
將Ph2PN(i-Pr)P(Ph)(i-Pr)-H(1.00公克,2.45毫莫耳)溶解在40毫升二乙醚。在室溫下,將二乙基鋅溶液(2.0毫升,在甲苯中的1.5M ZnEt2,3.00毫莫耳)添加至溶液中。在攪拌12小時之後,將溶液濃縮至20毫升。冷卻至-30℃得到無色固體。產量:0.800公克(65%)。分子量:501.92公克/莫耳[C26H34N2P2Zn]。分析計算值:C,62.22;H,6.83;N,5.58;P,12.34。實測值:C,62.71;H,6.80;N,6.03;P,12.29。熔點:95℃。1H-NMR(C6D6):δ=7.75-7.68(m,2H,芳基-H),7.65-7.56(m,H,芳基-H),7.44-7.35(m,2H,芳基-H),7.26-7.16(m,2H,芳基-H),7.10-6.90(m,8H,芳基-H),4.03-3.88(m,H,CHCH3),3.66-3.53(m,H,CHCH3),1.56-1.39(m,9H,CHCH3)1.38-1.31(m,3H,CH2CH3),1.31-1.27(m,3H CHCH3),0.73-0.62(m,2H,CH2CH3);13C-NMR(C6D6):δ=151.3,134.1,133.4,132.2,130.9,130.1,129.5,128.5,128.1(芳族),51.6,50.2(CHCH3),31.0,29.9,26.5,24.4(CHCH3),12.8(CH2CH3),2.9(CH2CH3);31P{H}NMR(C6D6):δ=87.50
(d,J=16.5Hz),28.00(d,J=16.5Hz)。
[Ph2PN(i-Pr)P(Ph)N(i-Pr)]2Mg之製備
將(Ph2PN(i-Pr)P(Ph)(i-Pr)-H(4.00公克,9.79毫莫耳)溶解在50毫升二乙醚中。在室溫下,將正丁基乙基鎂溶液(5.5毫升,在庚烷中的0.9M n-BuEtMg,4.95毫莫耳)添加至溶液中。將溶液再攪拌2小時。在冷卻至-30℃之後,獲得具有滿意的元素分析之無色晶體。產量:3.70公克(90%)。分子量:839.20公克/莫耳[C48H58MgN4P4]。元素分析:計算值:C,68.70;H,6.97;N,6.68;實測值:C,68.93;H,7.07;N,6.91。熔點:202℃。1H NMR(C6D6):δ=6.83-7.66(m,30H,芳基-H),3.54-3.62(m,2H,CHCH3),3.38-3.48(m,2H,CHCH3),1.51(d,J=6.5Hz,6H,CHCH3),1.19(d,J=6.5Hz,6H,CHCH3),1.15(d,J=6.5Hz,6H,CHCH3),1.10(m,6H,CHCH3);13C-NMR(C6D6):δ=143.4,142.0,134.9,133.4,132.5,131.5,129.4,128.6,128.0,127.9,127.1,125.2(芳族),52.0,51.5(CHCH3),29.5,28.6,25.9,24.1(CHCH3);31P{H}NMR(C6D6):δ=87.05(tr,J=10.4Hz),28.32(tr,J=10.4Hz)。
[Ph2PN(i-Pr)P(Ph)N(i-Pr)]2Cr之製備
將Ph2PN(i-Pr)P(Ph)(i-Pr)-H(4.00公克,9.79毫莫耳)溶解在40毫升甲苯中。在室溫下,將正丁基乙基鎂溶液(5.5毫升,在庚烷中的0.9M n-BuEtMg,4.95毫莫耳)添加至溶液中。將溶液再攪拌2小時且隨後過濾至CrCl2(THF)2(1.31公克,4.90毫莫耳)中。攪拌兩天得到紅-棕色懸浮液。在過濾及濃縮至10毫升之後,放置在-78℃下時獲得深色晶體。以戊烷清洗粉末狀晶體,獲得滿意的元素分析。產量:2.76公克(65%)。分子量:866.89公克/莫耳[C48H58CrN4P4]。分析計算值:C,66.50;H,6.74;Cr,6.00;N,6.46;P,14.29。實測值:C,66.28;H,6.43;Cr,6.20;N,6.31;P,14.69。熔點:161℃(分解)。
Ph2PN(i-Pr)P(Ph)N(i-Pr)-AlEt2.AlEt3之製備
將Et3Al(在甲苯中的1.9M Et3Al,10.0毫升,19毫莫耳)添加至溶解在甲苯(10毫升)中的(Ph2PN(i-Pr)P(Ph)(i-Pr)-H(3.7公克,9.06毫莫耳)。將溶液在50℃下加熱28小時。在真空中移除溶劑之後,剩餘無色油,將其以5毫升正己烷處理。藉由在真空中蒸發溶劑而剩餘無色殘餘物。從正己烷再結晶,得到無色材料。分子量:606.72公克/莫耳[C34H54Al2N2P2]。產量:4.86公克(95%)。元素分析:計算值:C,67.31;H,8.97;N,4.62;實測值:C,67.08;H,8.87;N,4.46。熔點:78℃(分解)。1H-NMR(C6D6):δ=-0.47(m,1H,J=8.1Hz,AlC
(H)HCH3),-0.21(m,1H,J=8.1Hz,AlC(H)HCH3),0.03(m,1H,J=8.1Hz,AlC(H)HCH3),0.16(m,1H,J=8.1Hz,AlC(H)HCH3),0.47(q,6H,J=8.1Hz,Al(CH2CH3)2),0.90(tr,3H,J=8.1Hz,AlCH2CH3),1.06(d,3H,J=6.7Hz,CHCH3),1.24(tr,3H,J=8.1Hz,AlCH2CH3),1.31(d,3H,J=6.7Hz,CHCH3);1.42(tr,3H,J=8.1Hz,AlCH2CH3),1.45(d,3H,J=6.7Hz,CHCH3),1.53(d,3H,J=6.7Hz,CHCH3),3.77(m,1H,CHCH3),4.16(m,1H,CHCH3),6.94-7.61(m,15H,C6H5);13C-NMR(CDCl3):δ=2.2,3.0(CH2CH3),9.6,10.6(CH2CH3),24.6,25.5,27.4,28.5(d,CHCH3),52.3,52.7(CHCH3),127.6,128.7,128.9,129.8,130.5,130.9,132.1,132.5,132.7,134.6,141.9,142.1(C6H5);31P{H}NMR(C6D6):δ=31.55(d,1JP-P=11.6Hz),91.00(d,1JP-P=11.6Hz)。
特定的PNPNH化合物之金屬化作用顯示於下文的方程式中,其中〝iPr〞為異丙基。
進行標準的乙烯低聚合作用(三聚合成1-己烯)且利用如上文製得的配位體。
測量平均活性、C6-產率、C6中之1-C6、
C10-產率及PE/蠟形成。將結果提出於表1中。
在表1中,顯示出取決於配位體Ph2PN(i-Pr)P(Ph)N(i-Pr)M之金屬的LAO產物分布及平均活性,其係與質子化配位體Ph2PN(i-Pr)P(Ph)N(i-Pr)H比較,其中系統為:配位體Cr(acac)3,改質劑[PPh4]Cl,在甲苯中的TEA。方法條件為:T=50℃,p=30巴,t=60分鐘,[Cr]=0.3毫莫耳/公升,[配位體]/[Cr]=1.25,[Al]/[Cr]=25,[Cl]/[Cr]=5。
總之,本文揭示乙烯之低聚合作用之方法,其包含將觸媒組成物與乙烯之氣相在有效使乙烯低聚合之條件下接觸,該條件較佳為1至200巴之壓力,更佳為10至50巴,從10至200℃之溫度,更佳為20至100℃,較佳為從20分鐘至20小時之平均滯留時間,較佳為1至4小時,其中觸媒組成物包含鉻化合物,較佳為其中鉻化合物係選自有機或無機鹽、配位錯合物、Cr(II)或Cr(III)之有機金屬錯合物,或包含前述中之至少一者的組合,更佳為其中鉻化合物為CrCl3(THF)3、乙醯丙酮Cr(III)、辛
酸Cr(III)、六羰基鉻、2-乙基-己酸Cr(III)和(苯)三羰基鉻,或包含前述中之至少一者的組合;金屬化PNPNH化合物,其中PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從PNPNH-結構中之一或多種組成化合物形成,較佳為任何環狀衍生物,其中P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從相同的PNPNH化合物中之兩種組成形成,較佳為其中R1、R2、R3、R4和R5係選自氯基、胺基、三甲基矽基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基、甲苯基和二甲苯基,更佳為其中PNPNH化合物為(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(第三丁基)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H,或包含前述中之至少一者的組合;及活化劑或共觸媒,較佳為三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、三氯三乙基化二鋁、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷,或包含前述中之至少一者的組合。
一種用於乙烯之低聚合作用之觸媒組成物包
含鉻化合物,較佳為其中鉻化合物係選自有機或無機鹽、配位錯合物、Cr(II)或Cr(III)之有機金屬錯合物,或包含前述中之至少一者的組合,更佳為其中鉻化合物為CrCl3(THF)3、乙醯丙酮Cr(III)、辛酸Cr(III)、六羰基鉻、2-乙基-己酸Cr(III)和(苯)三羰基鉻,或包含前述中之至少一者的組合;金屬化PNPNH化合物,其中PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從該PNPNH-結構中之一或多種組成化合物形成,較佳為任何環狀衍生物,其中P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從相同的PNPNH化合物中之兩種組成形成,較佳為其中R1、R2、R3、R4和R5係選自氯基、胺基、三甲基矽基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基、甲苯基和二甲苯基,更佳為其中PNPNH化合物為(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(第三丁基)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H,或包含前述中之至少一者的組合;及活化劑或共觸媒,較佳為三甲基鋁、三乙基鋁、三異丙基
鋁、三異丁基鋁、三氯三乙基化二鋁、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷,或包含前述中之至少一者的組合。
一種使以下通式之化合物金屬化之方法:R1R2P-N(R3)-P(R4)-N(R5)-H
其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中PNPN-H結構的P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從該PNPNH-結構中之一或多種組成化合物形成,較佳為任何環狀衍生物,其中P或N原子中之至少一者為環系統的一員,環系統係藉由取代而從相同的PNPNH化合物中之兩種組成形成,較佳為其中R1、R2、R3、R4和R5係選自氯基、胺基、三甲基矽基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基、甲苯基和二甲苯基,更佳為其中PNPNH化合物為(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(第三丁基)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H,或包含前述中之至少一者的組合,其中該方法包含以下步驟:將PNPNH化合物溶解在溶劑中,獲得溶液;使PNPNH化合物在溶液中金屬化,及使金屬化化合物沉澱、自溶劑分離且隨意地以溶劑清洗。
較佳為其中金屬化係藉由將有機金屬化合物、
含金屬之鹼、鈉金屬或鉀金屬以等於或超過PNPNH化合物之莫耳濃度的量添加至溶液中,更佳為其中金屬化作用係藉由添加下列者而達成:正丁基鋰、第二丁基鋰、第三丁基鋰、環戊二烯化鈉、氫化鈉、胺化鈉、鹵化烷基鎂或鹵化芳基鎂(格任亞試劑)、雙(三甲基矽基)胺化鈉、二烷基鎂、二芳基鎂、三烷基鋁、二烷基鋅、鈉金屬或鉀金屬(較佳為正丁基鋰),或包含前述中之至少一者的組合。
單數形式〝a〞、〝an〞和〝the〞包括複數指示對象,除非上下文另有其他明確的規定。〝或〞意指〝及/或〞。在本文所使用之技術及科學術語具有與熟諳本發明所屬之技術者通常瞭解的相同義意,除非另有其他定義。〝組合〞包括摻合物、混合物、合金、反應產物及類似者。
將所有引述之專利、專利申請案及其他參考文獻以其全文併入本文以供參考。然而,若本申請案中的術語與併入之參考文獻中的術語抵觸或衝突時,則以來自本申請案的術語優先於來自併入之參考文獻中的衝突術語。
在前述說明、申請專利範圍及圖中所揭示之特徵可為單獨或以其任何組合二者的其多樣形式為用以實現本發明的資料。
Claims (9)
- 一種乙烯之低聚合作用之方法,其包含將觸媒組成物與乙烯之氣相在有效使乙烯低聚合之條件下接觸,其中該觸媒組成物包含:(a)鉻化合物,(b)金屬化PNPNH化合物,其包含式PNPN-M之金屬化配位體,其中該PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中該PNPN-H結構的P或N原子中之至少一者為環系統的一員,該環系統係藉由取代而從該PNPNH-結構之一或多種組成化合物形成,其中,M為Li、Mg、Na、K、Cr、Al或彼等之組合,以及其中,取代係藉由每一組成化合物在形式上消除兩個完整的基團R1-R5或H、一個來自兩個基團R1-R5之各者或完整基團R1-R5之原子或H、及來自另一基團R1-R5之原子,及每一組成化合物以一個共價鍵連接在形式上因此產生價數不飽和位置以提供與最初存在於給定位置上相同的價數,(c)活化劑或共觸媒(cocatalyst),以及(d)式[H4E]X、[H3ER]X、[H2ER2]X、[HER3]X或[ER4]X之銨鹽或鏻鹽,其中E為N或P,X為Cl、Br或 I,及R係各自獨立地為C1-C22-烷基、C3-C10-環烷基、C1-C22-醯基、C6-C30-芳基、C2-C22-烯基、或C2-C22-炔基。
- 根據申請專利範圍第1項之方法,其中該低聚合作用係在1至200巴之壓力進行。
- 根據申請專利範圍第1項之方法,其中該低聚合作用係在從10至200℃之溫度進行。
- 根據申請專利範圍第1項之方法,其中該方法係連續或分批(batchwise)進行。
- 根據申請專利範圍第1項之方法,其中平均滯留時間係從20分鐘至20小時。
- 一種用於乙烯之低聚合作用之觸媒組成物,其包含:(a)鉻化合物,(b)金屬化PNPNH化合物,其包含式PNPN-M之金屬化配位體,其中該PNPNH化合物具有下式:R1R2P-N(R3)-P(R4)-N(R5)-H其中R1、R2、R3、R4和R5係獨立選自鹵素、胺基、三甲基矽基、C1-C10-烷基、經取代之C1-C10-烷基、C6-C20-芳基和經取代之C6-C20-芳基,或任何環狀衍生物,其中該PNPN-H結構的P或N原子中之至少一者為環系統的一員,該環系統係藉由取代而從該PNPNH-結構之一或多種組成化合物形成,其中,M為Li、Mg、Na、K、Cr、 Al或彼等之組合,以及其中,取代係藉由每一組成化合物在形式上消除兩個完整的基團R1-R5或H、一個來自兩個基團R1-R5之各者或完整基團R1-R5之原子或H、及來自另一基團R1-R5之原子,及每一組成化合物以一個共價鍵連接在形式上因此產生價數不飽和位置以提供與最初存在於給定位置上相同的價數,(c)活化劑或共觸媒,以及(d)改質劑,其中該改質劑係選自氯化四苯基鏻(tetraphenylphosphonium chloride)、氯化四乙基銨單水合物(tetraethylammonium chloride-monohydrate)、三乙胺鹽酸鹽(triethylamine-hydrochloride)、及氯化十二烷基三甲基銨(dodecyltrimethylammonium chloride)。
- 根據申請專利範圍第6項之觸媒組成物,其中該鉻化合物係選自有機或無機鹽、配位錯合物、Cr(II)或Cr(III)之有機金屬錯合物,或包含前述中之至少一者的組合。
- 根據申請專利範圍第6項之觸媒組成物,其中該鉻化合物為CrCl3(THF)3、乙醯丙酮Cr(III)、辛酸Cr(III)、六羰基鉻、2-乙基-己酸Cr(III)和(苯)三羰基鉻,或包含前述中之至少一者的組合。
- 根據申請專利範圍第6項之觸媒組成物,其中該活化劑或共觸媒係選自三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、三氯三乙基化二鋁(ethyl aluminum sesquichloride)、氯化二乙基鋁、二氯化乙基鋁、甲基鋁 氧烷(methyl aluminoxane),或包含前述中之至少一者的組合。
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